Lived experiences of bias in compensation and reintegration associated with false admissions of guilt.

Objective: Some exonerees receive compensation and aid after being exonerated of their wrongful convictions, and some do not. Looking beyond differences in state statutes, we examined possible reasons for biases in receiving compensation (via statutes or civil claims) and other reintegration services. More specifically, we examined how two unique types of false admission of guilt (i.

Wandering through quantum-mechanochemistry: from concepts to reactivity and switches.

Mechanochemistry has experienced a renaissance in recent years witnessing, at the molecular level, a remarkable interplay between theory and experiment. Molecular mechanochemistry has welcomed a broad spectrum of quantum-chemical methods to evaluate the influence of an external mechanical force on molecular properties. In this contribution, an overview is given on recent work on quantum mechanochemistry in the Brussels Quantum Chemistry group (ALGC).

PROTOCOL: Interview and interrogation methods and their effects on true and false confessions: An update and extension.

This is the protocol for a Campbell systematic review. The objective is to assess the effects of interrogation approach on confession outcomes for criminal (mock) suspects.

Mechanochemical Felkin-Anh Model: Achieving Forbidden Reaction Outcomes with Mechanical Force.

Anti-Felkin-Anh diastereoselectivity can be achieved for nucleophilic additions to α-chiral ketones upon stretching the ketone with a mechanical pulling force. Herein, a mechanochemical Felkin-Anh model is proposed for predicting the outcome of a nucleophilic addition to an α-chiral ketone. Essentially, the fully stretched chiral ketone has one substituent shielding each side of the carbonyl, in contrast to the Felkin-Anh model, in which free rotation around a bond is required to achieve the two rotamers of the ketone.

Conceptual density functional theory under pressure: Part I. XP-PCM method applied to atoms.

High pressure chemistry offers the chemical community a range of possibilities to control chemical reactivity, develop new materials and fine-tune chemical properties. Despite the large changes that extreme pressure brings to the table, the field has mainly been restricted to the effects of volume changes and thermodynamics with less attention devoted to electronic effects at the molecular scale. This paper combines the conceptual DFT framework for analyzing chemical reactivity with the XP-PCM method for simulating pressures in the GPa range.

A Quantum Chemical Deep-Dive into the π-π Interactions of 3-Methylindole and Its Halogenated Derivatives-Towards an Improved Ligand Design and Tryptophan Stacking.

Non-covalent π-π stacking interactions often play a key role in the stability of the secondary and tertiary structures of peptides and proteins, respectively, and can be a means of ensuring the binding of ligands within protein and enzyme binding sites. It is generally accepted that minor structural changes to the aromatic ring, such as substitution, can have a large influence on these interactions. Nevertheless, a thorough understanding of underpinning phenomena guiding these key interactions is still limited.

Designing Force Probes Based on Reversible 6π-Electrocyclizations in Polyenes Using Quantum Chemical Calculations.

The conjugated π-system in polyenes can be interrupted by electrocyclic ring-closure reactions. In this work, this 6π-electrocylization is shown by means of density functional calculations to be reversible by the application of an external mechanical pulling force at the terminal ends of the interrupted polyene chain. The test systems were constrained in a fused ring system, thus locking the orientation of three π-bonds and generally promoting 6π-electrocyclic ring-closure reactions.

Mechanochemically Triggered Topology Changes in Expanded Porphyrins.

A hitherto unexplored class of molecules for molecular force probe applications are expanded porphyrins. This work proves that mechanical force is an effective stimulus to trigger the interconversion between Hückel and Möbius topologies in [28]hexaphyrin, making these expanded porphyrins suitable to act as conformational mechanophores operating at mild (sub-1 nN) force conditions. A straightforward approach based on distance matrices is proposed for the selection of pulling scenarios that promote either the planar Hückel topology or the three lowest lying Möbius topologies.

Alkaline Earth Metals Activate N and CO in Cubic Complexes Just Like Transition Metals: A Conceptual Density Functional Theory and Energy Decomposition Analysis Study.

Following the recent discovery of stable octa-coordinated alkaline earth metals with N and CO, the role of group II metals in the catalytic reduction of these ligands by means of density functional theory (DFT) calculations and conceptual DFT-based reactivity indices is investigated. Cubic group IV and octahedral group VI transition metal complexes as well as the free ligands are computed for reference. The outer and most accessible atoms of N and CO become much more nucleophilic and electrophilic in all complexes, relevant for N fixation, as probed by the Fukui function and local softness.

Ambident Nucleophilic Substitution: Understanding Non-HSAB Behavior through Activation Strain and Conceptual DFT Analyses.

The ability to understand and predict ambident reactivity is key to the rational design of organic syntheses. An approach to understand trends in ambident reactivity is the hard and soft acids and bases (HSAB) principle. The recent controversy over the general validity of this principle prompted us to investigate the competing gas-phase S 2 reaction channels of archetypal ambident nucleophiles CN , OCN , and SCN with CH Cl (S 2@C) and SiH Cl (S 2@Si), using DFT calculations.

The hunt for reactive alkynes in bio-orthogonal click reactions: insights from mechanochemical and conceptual DFT calculations.

In our effort to implement the mechanical force used to activate single molecules in mechanochemistry in the context of conceptual density functional theory, we present a theoretical investigation of strained alkynes for rationalizing structural trends as well as the reactivity of cyclic alkynes that are of great importance in click reactions. The strain on the triple bond in cyclic alkynes is modeled by angular constraints in a 2-butyne fragment and the corresponding bending force is calculated by means of an extended COGEF (constrained geometries simulate external forces) model. In general, the force required to bend the triple bond is smaller with electron-withdrawing groups on the propargylic C-atom, which elegantly results in smaller angles around the triple bond in cyclic alkynes with such substitution pattern.

Implementing the mechanical force into the conceptual DFT framework: understanding and predicting molecular mechanochemical properties.

In molecular mechanochemistry, the chemical properties of a reactant system are modified through the absorption of mechanical energy at the single molecular level, as opposed to thermochemistry (heat), electrochemistry (electrical current) and photochemistry (light). In this proof-of-concept paper, we present a theoretical approach to rationalize and predict the change in chemical properties and concepts when an external stretching force, Fext, is applied to a chemical bond. By considering perturbations to the total molecular energy due to Fext, a series of mechanochemical response indices are obtained within the framework of conceptual density functional theory (DFT).